United States Patent (19) 11 4,407,955

Muller et al. (45) Oct. 4, 1983

(54) FERMENTABLE SUGAR FROM THE 56) References Cited
HYDROLYSIS OF STARCH DERVED FROM U.S. PATENT DOCUMENTS
DRY MILLED CEREAL GRANS
4,330,625 5/1982 Miller et al. ........................ 435/16
75 Inventors: Werner C. Muller, Dobbs Ferry, Primary Examiner-William F. Smith
N.Y.; Franklyn D. Miller, Cincinnati, Attorney, Agent, or Firm-Kenneth D. Tremain
Ohio 57 ABSTRACT
73 Assignee: National Distillers and Chemical
Starch derived from a dry milled cereal grain such as
corn or milo is hydrolyzed to provide a sterile aqueous
Corporation, New York, N.Y. fermentable sugar solution which is especially adapted
for fermentative conversion to ethanol with minimum
* Notice: The portion of the term of this patent thermal expenditure. Following a preliminary acid-cat
subsequent to May 18, 1999 has been alyzed hydrolysis of the starch to provide a sterile hy
disclaimed. drolysate slurry, the slurry is further hydrolyzed in the
presence of added aqueous non-fermentable carbohy
drate to reequilibrate the hydrolysis reaction in favor of
(21) Appl. No.: 320,278 increased production of fermentable sugar, primarily
glucose. Substantially all of the water insoluble protein
(22 Filed: Nov. 12, 1981 and oil components, and a portion of the water.soluble
components, e.g., sugars, proteins and vitamins, are
separately recovered from the sterile hydrolysate either
51) Int. Cl. ........................... C13K 1/06; C12P 7/06 before or after the further hydrolysis step with the
52 U.S.C. ...................................... 435/161; 127/38; water solubles being recycled to the system to effect
127/40; 203/19; 203/DIG. 13 reequilibration of a further quantity of hydrolysate.
58 Field of Search ....................... 127/37, 38, 39, 40;
435/161; 203/19, DIG. 13 14 Claims, 1 Drawing Figure

92ETHANOL
U.S. Patent Oct. 4, 1983 4,407,955

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 1. 4,407,955 2
FERMENTABLE SUGAR FROM THE
operations involved in the manufacture of ethanol from
vegetative sources.
HYDROLYSIS OF STARCH DERVED FROM ORY Processes for the acid hydrolysis of carbohydrate
MILLED CEREAL GRANS polymers, i.e., starch and cellulose, to provide ferment
REFERENCE TO RELATED APPLICATIONS able sugars are known (viz., U.S. Pat, Nos. 2,203,325;
2,210,659; 2,359,763; 2,393,095; 2,395,907; 2,529,131;
This application discloses subject matter which is 2,565,404; 2,946,706; 2,954,304; 2,989,425; 3,169,083;
disclosed and claimed in commonly assigned copending 3,200,012; 3,236,687; 3,313,654; 3,446,664; 3,484,287;
U.S. patent application Ser. Nos. 091,640 filed Nov. 5, 3,607,395; 4,137,094 and 4,155,884). While these and
1979, now abandoned in favor of copending U.S. patent 10 similar processes are for the most part readily adaptable
application Ser, No. 237,038, filed Feb. 23, 1981, to the hydrolysis of the finely divided, relatively pure
219,011 filed Dec. 22, 1980, now abandoned in favor of starch derived from conventional processes of wet mill
copending U.S. patent application Ser. No. 391,324 filed ing cereal grains, their application to the starch-contain
June 23, 1982, and U.S. patent application Ser, No. ing fractions obtained from processes of dry milling
320,277 filed Nov. 12, 1981 filed of even date herewith, 15 cereal grains as currently practiced would be uneco
BACKGROUND OF THE INVENTION nomically wasteful of the protein and edible oil associ
ated with these fractions which in the case of corn and
This invention relates to the acid hydrolysis of starch milo, is especially significant. Wet milling processes
derived from dry milled cereal grains such as corn and typically remove all but an insignificant amount of non
milo to provide fermentable sugar, 20
With the ever-increasing depletion of economically starch materials, i.e., protein, cellulosic fiber and oil,
recoverable petroleum reserves, the production of etha from the starch component of the grain, the non-starch
materials finding valuable application in their own right
nol from vegetative sources as a partial or complete as
replacement for conventional fossil-based liquid fuels theanimal feeds and feed supplements. However, from
becomes more attractive. In some areas, the economic sugar, the sugarofto producing
25 standpoint
dilute
starch for conversion to
ethanol and the dilute ethanol
and technical feasibility of using a 90% unleaded gaso to essentially anhydrous ethanol, conventional wet-mill
line-10% anhydrous ethanol blend ("gasohol") has ing
shown encouraging results. According to a recent ultimately remove the large amounts of processneed
processes are undesirable because of the to
water
study, gasohol powered automobiles have averaged a involved.
5% reduction in fuel compared to unleaded gasoline 30
powered vehicles and have emitted one-third less car minimal Where, as in the case of low cost industrial ethanol, a
bon monoxide than the latter. In addition to offering use of energy is necessary to achieve an eco
promise as a practical and efficient fuel, biomass nomically viable process, a relatively energy and capital
derived ethanol in large quantities and at a competitive intensive process such as one based on wet-milled corn
price' has the potential in some areas for replacing cer 35 starch as the starting material can be disadvantageous.
tain petroleum-based chemical feedstocks. Thus, for For this reason, the hydrolytic conversion of starch
example, ethanol can be catalytically dehydrated to derived from any of the known and conventional dry
ethylene, one of the most important of all chemical raw milling processes is especially desirable in an industrial
materials both in terms of quantity consumed and versa scale anhydrous ethanol operation since dry milling
tility in product synthesis, 40 processes employ no added water beyond the moisture
The various operations in processes for obtaining which is already naturally present in the grain. Thus, for
ethanol from such recurring sources as cellulose, cane example, in a typical dry corn milling process, the ker
Sugar, amylaceous grains and tubers, e.g., the separation nels are broken by impact and the resulting fractions
of starch granules from non-carbohydrate plant matter made up of grits and fine feed which contain the bulk of
and other extraneous substances, the chemical and/or 45 the starch and significant quantities of oil, protein, and
enzymatic hydrolysis of starch to fermentable sugar cellulosic fiber, germ which contains most of the oil
(liquefaction and saccharification), the fermentation of content of the kernels, and hulls which contain the
sugar to a dilute solution of ethanol ('beer') and the major portion of the fiber, are separated employing
recovery of anhydrous ethanol by distillation, have degerminators, sifters, aspirators and gravity separators,
been modified in numerous ways to achieve improve SO A typical dry corn milling product analysis (pounds per
ments in product yield, production rates and so forth
(see, for example, U.S. Pat, No. 3,236,740 and the book bushel) is as follows:
let "Industrial Alcohol by Continuous Fermentation
and Vacuum Distillation With Low Energy Consump ANALYSIS ON YELLOW CORN #2,
tion', of Chemapec, Inc., Woodbury, N.Y.). For etha 55 STREAM LB/100 LB (DRY BASIS)
CORN GERM BRAN GRITS
nol to realize its vast potential as a partial or total substi
tute for petroleum fuels or as a substitute chemical feed Starch Protein
34.27
4.28
1.33
0.64
1.14
0.27
31.80
3.37
stock, it is necessary that the manufacturing process be Oil 2.05 1.05 0.17 0,83
as efficient in the use of energy and raw materials as Fiber 1.22 0.21 0.57 0.44
possible so, as to maximize the energy return for the 60 Nitrogen-Free Extract 5.00 0.21 0,5 0.4
amount of ethanol and enhance the standing of the Ash 0.77 1.32 150 2.18
ethanol as an economically viable replacement for pe Moisture Dry Solids 47.59
8.41
4.76
0.84
3.80
0.68
39,03
6,89
troleum based raw materials. To date, however, rela
tively little concern has been given to the energy and TOTAL 56,00 5.60 4.48 45.92
raw material requirements for manufacturing ethanol 65
from biomass and consequently, little effort has been As this analysis indicates, the grits contain 92.8% of
made to minimize the thermal expenditure and waste the starch, 78.7% of the protein and 40.5% of the oil of
incurred in carrying out any of the aforesaid discrete the whole corn kernels, Direct complete hydrolysis of
 3
4,407,955
4.
the grits would therefore make these substantial 219,011, filed Dec. 22, 1980, now abandoned in favor of
amounts of protein and oil unavailable for use as comes copending U.S. patent application Ser. No. 391,324 filed
tibles. June 23, 1982, which is incorporated by reference
Accordingly, there has heretofore existed a need for herein describes a dry milling process which is espe
a process for converting starch derived from dry milled cially advantageous for use in the present invention. An
cereal grains to fermentable sugars while recovering aqueous slurry of the dry milled starch, preferably one
substantially all of the protein and oil content of the which has been prepared with stillage obtained from an
starch component of the dry milled grain prior to the ethanol concentration facility and/or repulp superna
complete hydrolysis of the starch. The term "cereal tant as hereinafter described, is subjected to a prelimi
grain' as used herein is to be understood in its com 10 nary acid catalyzed hydrolysis, advantageously in ac
monly used sense and is inclusive of all varieties of corn cordance with the process described in Ser. No.
(maize), milo, wheat, rice, and the like. 091,640, filed Nov. 5, 1979, now abandoned in favor of
In addition to the foregoing consideration, it is copending U.S. patent application Ser. No. 237,038,
known that besides the desired reaction whereby the filed Feb. 23, 1981, which is incorporated by reference
carbohydrate polymer molecules are split into frement 15 herein (employing, inter alia, elevated pressure and
able sugars, other reactions taking place during hydro temperature), to provide a sterile partial hydrolysate.
lysis tend to reduce the maximum theoretical conver This partial hydrolysate, which contains a water insolu
sion of available carbohydrate to such sugars and pro ble phase made up of water insoluble protein and oil and
duce non-fermentable hydrolysate product. Three of a water soluble phase made up of fermentable sugars,
the principal types of undesirable reactions known to 20 partial hydrolysates and other water soluble compo
take place in acid catalyzed carbohydrate polymer hy nents of the starch, is then preferably subjected to a
drolysis are: degradation (starch molecule is irrevers partial pressure and temperature reduction with the
ibly destroyed to provide 5-hydroxymethylfurfural steam thus generated advantageously being used in
which hydrolyzes to levulinic acid and formic acid, and some other capacity in the process, e.g., to preheat
separately to humins); reversion (glucose repolymerizes 25 water, stillage and/or repulp supernatant used in pre
and/or isomerizes to unfermentable substances); and paring the aqueous starch slurry. As a result of the
retrogradation (hydrolysis splits out the branched chain aforesaid preliminary hydrolysis step, the proteins origi
components of the starch molecule leaving a straight nally present in the starch undergo modification
chain, lower molecular weight water insoluble poly thereby facilitating their later separation and recovery
meric molecule which crystallizes at about 70-80 C. 30 from the hydrolysate by centrifugation. The partial
and becomes resistant to further hydrolysis). In a typi hydrolysate, optionally at reduced pressure and temper
cal acid hydrolysis process, when equilibrium has been ature, is thereafter subjected to a further and final hy
achieved, from about 15 to about 20 weight percent of drolysis in the presence of aqueous water soluble non
the depolymerized starch will be present in the form of fermentable carbohydrate, e.g., any of the degradation,
one or more of the foregoing non-fermentable hydroly 35 reversion and/or retrogradation products referred to
sates, the balance of the depolymerized starch being above, whereby a sterile, substantially fully hydrolyzed
present as glucose and/or other fermentable sugar(s). starch slurry of high fermentable sugar content is ob
To the extent non-fermentable products are produced tained. The presence of aqueous water soluble non-fer
side-by-side with fermentable sugar(s), they represent a mentable carbohydrate (which is recovered as stillage
loss in yield of the hydrolysis reaction and compromise and/or as repulped supernatant from the conversion of
the usefulness of acid hydrolysis as a process for obtain a previous quantity of starch to concentrated ethanol) at
ing fermentable sugar on a large-scale, economical ba the commencement of the final hydrolysis step provides
S1S. several very significant advantages each of which re
According to U.S. Pat. No. 2,529, 121 referred to sults in a greater overall production of fermentable
supra, the non-fermentable hydrolysate products result 45 sugar when a steady-state process has been achieved.
ing from one or more of the aforesaid undesirable reac For one, the presence of non-fermentable carbohydrate
tions eventually is recovered in the stillage, or "vin during final hydrolysis reequilibrates the hydrolysate
nasse', obtained as a result of the distillation of the with the result that higher conversion levels of partial
dilute ethanol, or "beer', resulting from the fermenta hydrolysate to fermentable sugar are obtained. For
tion of the fermentable sugar portion of the hydrolysate. 50 another, the addition of more water (the solvent me
To maximize overall ethanol production based on the dium for the non-fermentable carbohydrate) to the par
original quantity of carbohydrate polymer employed, it tial hydrolysate lowers its solids content whereby the
is proposed in U.S. Pat. No. 2,529,131 to subject the equilibrium of the final hydrolysis reaction is shifted still
stillage to further acid hydrolysis to convert the unfer further to the production of fermentable sugar. Follow
mentable products therein to fermentable sugars. 55 ing final hydrolysis, the starch hydrolysate is preferably
SUMMARY OF THE INVENTION subjected to further pressure and temperature reduc
tion, the generated steam values likewise advanta
In accordance with the present invention, a process is geously being used in some other useful capacity. The
provided for converting starch derived from dry milled sterile hydrolysate slurry is then separated into an aque
whole grain, which starch contains varying amounts of 60 ous portion containing fermentable sugars, primarily
water insoluble protein and oil depending upon the glucose, and a part of the water soluble components and
nature of the grain, and which are relatively substantial a water insoluble protein and oil (and fiber, if originally
in the case of corn and milo, and relatively small present) portion containing the remaining part of the
amounts of one or more water soluble components water soluble components. The aforesaid aqueous solu
selected from the group consisting of sugar, protein, 65 tion of fermentable sugar, following neutralization of
vitamin and mineral, to fermentable sugar to provide the acid therein with a base such as ammonia, alkali
substrate for the thermally efficient large-scale produc metal hydroxide, alkaline earth metal hydroxide, or the
tion of ethanol. U.S. patent application Ser. No. like, is then conveyed to a fermentation unit where
 5
4,407,955
6
conversion of the sugar to ethanol and further hydroly grits can vary widely, it is preferred to use only so much
sis of any partial starch hydrolysate present therein to water as is necessary to achieve a pumpable slurry so as
fermentable sugar takes place (when saccharifying en to minimize the amounts of water which must later be
zyme is present). It is also within the scope of this inven removed in the downstream fermentation ethanol con
tion to remove the protein, oil and/or fiber from the 5 centration facility. Slurries containing from about 20%
partial hydrolysate prior to subjecting the latter to final to about 50% starch, and preferably from about 30% to
hydrolysis. about 40% starch (dry solids), by weight of the entire
The previously separated water insoluble protein and slurry are generally readily manageable by most con
oil portion may be diluted or repulped with water or ventional pumping equipment. Following the slurrying
stillage to dissolve the water soluble components associ- 10 operation, the acidified aqueous slurry of starch passing
ated therewith with the resulting aqueous slurry there through line 15 is pressurized and raised to a tempera
after being separated into a protein and oil portion sub ture of about 75 C. by heater 16 and thereafter mixed
stantially free of any of the water soluble components of with high pressure steam introduced through line 17.
the original starch and starch hydrolysate, and an aque Hydrolysis of the starch to partial hydrolysate and some
ous portion containing most of the water soluble com- 15 fermentable sugar thereafter occurs in preliminary hy
ponents. The protein and oil may be used directly in drolysis unit 18. The pressure imparted to the starch
animal feed or, if desired, they may be separately recov slurry can vary over fairly wide limits but in any event
ered for individual use. The aqueous portion containing must be a pressure which is in excess of the saturation
water soluble components of the starch, i.e., repulped pressure of water at the temperature of the hydrolysate
supernatant, is advantageously recycled for use in the 20 stream passing through line 19, preferably by at least
aforedescribed final hydrolysis step.
Employing the foregoing starch hydrolysis process, about 50 psig, Pressures on the order of from about 100
to about 1,000 psig and advantageously, from about 600
only minimal quantities of fresh water need be used to to about 900 psig, generally provide good results. The
accomplish conversion of the starch to fermentable amount of steam delivered to the starch slurry through
sugar thus reducing the amount of water which must be 25 line 17 should be sufficient to increase the temperature
removed from product ethanol obtained from the fer of the slurry to within the range of from about 140 C.
mentation of the sugar, and consequently, the amount of to about 220 C. and preferably from about 160 C. to
thermal energy which must be expended in the manu about 200° C. Residence time of the starch slurry in
facture of the ethanol. Since substantially all of the hydrolysis unit 18 to effect substantial hydrolysis and
water insoluble protein contained in the original starch 30 sterilization of the starch is not a critical consideration.
can be recovered for other commercially valuable uses, In general, residence times of just a few seconds, e.g.,
notably animal feed, and due to the water recycle fea from about 5-10 seconds, to 10 minutes or more, pro
ture which is made possible by the process herein, a vide good results. Under the foregoing conditions of
good portion of the water soluble components of the hydrolysis, the accompanying water insoluble protein
starch are retained in the solution of product ferment- 35 will undergo modification facilitating its efficient recov
able sugar and are therefore available for satisfying ery by such conventional means as centrifugation. The
certain nutrient requirements of the yeast employed in hydrolyzed starch slurry is then conveyed through line
the fermentation of the sugar to ethanol. 19 to a first optional pressure reduction vessel 20 in
BRIEF DESCRIPTION OF THE DRAWING 40 which a partial pressure reduction takes place to par
tially cool the slurry for the subsequent equilibration
The accompanying drawing is a diagrammatic flow step. In the embodiment of the process shown in the
sheet illustrative of the starch hydrolysis process of the drawing, steam generated by the foregoing partial pres
present invention as applied to conventionally dry sure reduction operation recovered through line 21 is
milled, dehulled, degerminated corn grits which, as advantageously passed through a heat exchanger to
shown above, contains the major amount (i.e., typically 45 pre-heat the stillage and/or the repulp supernatant
over 93%) of the starch originally present in the whole Streans.
corn, together with lesser quantities of protein, oil and The cooled, partially depressurized slurry is then
fiber. The process contemplates the use of known and conveyed through line 22 to an optional second pres
conventional equipment which is readily available from sure reduction vessel 23 where the pressure is let down
several suppliers. 50 further, advantageously to atmospheric level. Gener
DESCRIPTION OF THE PREFERRED ated steam recovered through line 22a is likewise uti
EMBODIMENTS lized in some other useful capacity. The depressurized
slurry emerging from vessel 23 through line 24 is intro
Referring to the drawing, dry milled corn grits at duced into a first separator unit 25, preferably a centri
ambient temperature and pressure passing through line 55 fuge, with the sterile aqueous fermentable sugar super
10 is slurried with water, preferably in the form of stil natant recovered therefrom through line 26 being mixed
lage flowing through line 11 and/or repulp supernatant with stillage flowing through line 27 and optionally
flowing through line 12, into stirred starch slurry tank with high pressure steam through line 28 prior to intro
13. An aqueous solution of sulfuric acid (98% acid by duction into final hydrolysis unit 29. Quantities of steam
weight) is introduced into starch slurry tank 13 through 60 and operating pressures of final hydrolysis unit 29 can,
line 14. Good results can be achieved with other acids, if desired, be similar to those previously described in
e.g., hydrochloric, phosphoric, nitric, etc., in amounts connection with the operation of preliminary hydrolysis
sufficient to provide an acidified starch slurry having a unit 18. Alternatively or in addition to stillage, the su
pH of from about 1.0 to about 2.5. Stillage is available in pernatant in line 26 can be mixed with repulp superna
generous quantities from the ethanol distillation opera- 65 tant flowing through line 12. The amount of stillage/-
tion and repulp supernatant is provided as a result of the repulp supernatant added to the initial hydrolysate can
protein and oil separation procedures hereinafter more vary widely but in general, will be an amount which,
fully described. While the amount of water added to the because of the reequilibrating effect of the non-ferment
 4,407,955
7 8
able carbohydrate therein, will result in the production charged from the scrubber through line 42. Stillage
of significantly greater quantities of fermentable sugar, from the rectifier column is recovered therefrom
mostly glucose, than would be obtained in the absence through line 42 with part being purged through line 43
of stillage/repulp supernatant. Thus, instead of a finai as required. The remaining stillage may then be divided
dextrose equivalent (D.E.) of about 75-80 which would into streams 11 for slurrying corn grits and/or line 27
result from a conventional acid hydrolysis process, the for use in hydrolysis as previously described. The un
addition herein of stillage/repulp supernatant in final derflow, or "mud', recovered from separator unit 25
hydrolysis unit 29 results in a significant increase in through line 44 is repulped with water, preferably stil
D.E. levels, e.g., from about 85 to 95 and even higher. lage, supplied through line 46 in repulp vessel 45 and
Emerging from final hydrolysis unit 29 through line 30, 10 the repulped liquid, containing oil, water insoluble pro
the hydrolysate or "sugar liquor' is depressurized as tein and some water soluble components, is introduced
required in a series of pressure reduction units 31 and 32 through line 47 into a second separator unit 48, prefera
which operate substantially in the same manner as pres bly a centrifuge, with the repulp supernatant (i.e., the
sure reduction units 20 and 23. The hydrolysate emerg water soluble component(s)-containing phase) flowing
ing from pressure reduction unit 32, now at its maxi 15 through line 12 being optionally combined with stillage
mum fermentable sugar content for the conditions flowing through line 11, the combined streams thereaf
chosen, is combined with an amount of base, e.g., am ter being used in the slurrying operation and/or hydro
monia or ammonium hydroxide, supplied through line lysis steps as previously described. The underflow, or
33 to reduce the pH of the hydrolysate to a level suit "mud', recovered from separator 48 is discharged
able for optimum fermentation, e.g., to about pH 4.0, 20 through line 49. This mud contains all of the protein and
and the neutralized hydrolysate is then passed through oil, together with residual quantities of carbohydrates,
line 34 into fermentation unit 35 for conversion of the present in the original corn grits and as such constitutes
sugar to ethanol. When the salt resulting from neutral (when dried) a nutritious animal feed or feed supple
ization of the acid is recycled (as will be the case when ment.
stillage and/or repulped supernatant is added to the 25 The following represents a material balance (lb/hr)
starch slurry/partial starch hydrolysate), a buffering for various stages of the process herein.
ACID HYDROLYSIS OF CORN GRITS TO PROVIDE STERILE
AQUEOUS FERMENTABLE SUGAR AND PROTEIN/OIL BY-PRODUCT
STREAM (Corresponding to the Drawin
(Prior to Mixture (After Mixture
COMPONENT O 27 12 15 with Steam) 15 with Steam)
Water/Steam 18,259.00 130,617.31 64,420.43 182,079.19 308,949.50
Ethanol - 44.86 2.24 36.59 36.59
Glycerol --- 15,167.17 756.79 12,374.00 12,374.00
Starch 84,270.00 -- - 84,269.87 84,269.87
Fermentable Sugar - 93.54 3,413.55 3,485.17 3,485.17
Non-Fermentable Sugar 3,763.00 9,573.36 3,413.55 14,506.44 14,506.44
Protein 12,297.00 376.83 73.92 12,659.42 12,659.42
Extractables 3,101.00 12,935.44 847.45 13,856.18 13,856.18
Sulfuric Acid - - 178.75 178.75 2,922,58
Ammonia - -- - --

Ammonium Sulfate - 15,393.57 768.27 2,561.95 12,561.99

Live Yeast -- - - -

Dead Yeast - 884.63 44.14 72.76 721.76

Vitamins - 0.04 - 0.04 0.04
Carbon Dioxide - 0.01 H 0.01 O.O1
TOTAL 121,690.00 185,086.50 73,918.94 337,329.06 466,343.19

action results so that it becomes necessary to add still

higher levels of acid to achieve a pH which is appropri
ate for hydrolysis. Such higher levels of acid eventually 50 ACID HYDROLYSIS OF CORN GRITS
result in the production of still more salt which results TO PROVIDE STERILE
in an even greater buffering action. Accordingly, it may AQUEOUS FERMENTABLE SUGAR AND
be advantageous to contact the stillage and/or repulp PROTEIN/OIL BY-PRODUCT
supernatant with a strong acid cation exchange resin, STREAM (Corresponding to the Drawing)
e.g., Dow's Dowex MWA-1 and XFS-4066 which are 55 COMPONENT 19 21 24 44
copolymers of styrene and divinylbenzene with con Water/Steam 299,587.12 50,734.82 248,852.25 22,775.59
trolled crosslinkage, in order to remove cations, e.g., Ethanol 36.59 r- 36.59 3.35
NH4+, and regenerate acid. Dilute aqueous ethanol Glycerol 12,374.00 - 12,374.00 1,132.50
Starch 0.06 - 0.06 0.01
resulting from fermentation is introduced through line Fermentable 55,811.87 - 55,811.87 5, 108.05
36 into a rectifier column 37 for concentration to high 60 Sugar
proof, e.g., 192' ethanol. The ethanol-containing carbon Non-Fermentable
Sugar
55,811.87 --- 55,811.87 5,108.05
dioxide vapor produced in fermentation unit 35 is ad Protein 12,659.42 - 12,659.42 12,292.97
vantageously passed through line 38 to stripper column Extractables 13,856.18 - 13,856.18 1,268.15
39 fed with cold water through line 40. The water pass Sulfuric Acid 2,922.58 - 2,922.58 267.48
ing downwardly through the stripper absorbs most of 65 Ammonia - - - -

the ethanol present in the incoming aqueous stream and Ammonium

Sulfate
2,561.99 - 12,561.99 1,149.71
the resulting aqueous stream is introduced into rectifier Live Yeast -- - re- -

column 37 through line 4, carbon dioxide being dis Dead Yeast 72.76 - 721.76 66.06
 4,407,955
10
-continued containing water insoluble protein and oil and
ACID HYDROLYSIS OF CORN GRITS
water soluble components;
TO PROVIDE STERILE (b) separating water insoluble protein and oil with or
AQUEOUS FERMENTABLE SUGAR AND without water soluble components from the hy
PROTEINAOIL BY-PRODUCT drolysate resulting from step (a); and,
STREAM (Corresponding to the Drawing) (c) hydrolyzing in a further hydrolysis step the aque
COMPONENT 19 21 24 44 ous sterile starch hydrolysate slurry resulting from
Vitamins 0.04 0.04 step (a) in the presence of added aqueous water
Carbon Dioxide 0.01 w 0.01 -- soluble non-fermentable carbohydrate to provide a
TOTAL 466,343.12 50,734.82 415,608.25 49,171.89 O sterile aqueous solution of fermentable sugar.
2. A process for converting the starch fraction de

ACID HYDROLYSES OF CORN GRITS TO PROVIDESTERILE

AQUEOUS FERMENTABLE SUGAR AND PROTEIN/OIL BY-PRODUCT
STREAM (Corresponding to the Drawing)
(Prior to Mixture (After Mixture
with Stillage with Stillage
COMPONENT 46 47 . 49 26 and Steam) 26 and Steam)
Water/Steam 73,632.56 96,399.12 31,978,71 226,076.50 356,693.94
Ethanol - 3.35 1.1 33.24 78.11
Glycerol 1,32.50 375.69 11,241.49 26,408.66
Starch w 0.01 ww. 0.06 0.07
Fermentable Sugar m 5,108.05 1,694.50 50,703.82 50,797.36
Non-Fermentable Sugar w 5,108.05 1,964.50 50,703.82 60,277. 9
Protein 12,292.97 12,219.03 366,44 743.27
Extractables 1,268.15 420,69 12,588.03 25,523.48
Sulfuric Acid 267.48 88,73 2,655, 10 2,655.0
Ammonia re- e
Ammonium Sulfate 1,149.71 38139 11,412.27 26,805.85
Live Yeast w
Dead Yeast 66,06 1.91 655.0 1,540.33
Vitamins - re- awa 0.03 0.08
Carbon Dioxide o 0.0 0.02
TOTAL 73,623.56 122,795.06 48,876.26 366,436,12 551,523.12

35
ACID HYEOROLYSIS OF CORN GRTS rived from whole dry milled cereal grain to a sterile
TO PROVIDE SERILE aqueous solution of fermentable sugar, said starch con
AQUEOUS FERMENTABLE SUGAR AND taining water insoluble protein and oil, which com
PROTEINAOIL BY-PRODUCT prises:
STREAM (Corresponding to the Drawing) 40 (a) hydrolyzing in a preliminary hydrolysis step an
COMPONENT 30 33 34 aqueous slurry of the starch in the presence of an
Water/Steam 356,693.87 - 261,516.87 100,000.00 acid hydrolysis catalyst at an elevated pressure and
Ethanol
Glycerol
78.11
26,408.66
-
-
78.11
26,408.66 11,617.23
34.35 temperature to provide a starch hydrolysate slurry
Starch containing water insoluble protein and oil and
Fermentable 92,191.81 - 92,191.81 71.62 45 water soluble components;
Sugar (b) hydrolyzing in a further hydrolysis step the aque
Non-Fermentable 8,882.62 - 18,882.62 7,329.91 ous sterile starch hydrolysate slurry resulting from
Sugar
Protein 743.27 - 743.27 28852 step (a) in the presence of added aqueous water
Extractables 25,523.48 - 25,523.48 9,907.76 soluble non-fermentable carbohydrate to provide a
Sulfuric Acid 2,655.10 - 2,655,10 w 50 sterile aqueous solution of fermentable sugar; and
Ammonia
Ammonium 26,805.85
92.05 921.05
26,805,85 11,793.74
e - (c) separating water insoluble protein and oil with or
Sulfate without water soluble components from the hy
Live Yeast --- w w drolysate resulting from step (b).
Dead Yeast
Vitamins
1540.33
0.08
-
-
1,540.33
0.08
677.62
0.03 55
3. The process of claim 1 or 2 wherein step (c) is
Carbon Dioxide 0.02 -- 0.02 0.01
carried out at an elevated pressure and temperature
TOTAL 551,552.94. 921.05 457,266.94 14,720.44
which is less than the pressure and temperature of step
(a).
4. The process of claim 1 or 2 wherein the cereal
What is claimed is: grain feed for hydrolyzing step (a) is corn or milo.
1. A process for converting the starch fraction de 60 5. The process of claim 1 or 2 wherein the cereal
rived from whole dry milled cereal grain to a sterile grain feed for hydrolyzing step (a) is dehulled corn or
aqueous solution of fermentable sugar, said starch con milo.
taining water insoluble protein and oil, which com 6. The process of claim 1 or 2 wherein the cereal
prises: grain feed for hydrolyzing step (a) is degerminated corn
(a) hydrolyzing in a preliminary hydrolysis step an 65 or milo.
aqueous slurry of the starch in the presence of an 7. The process of claim 1 or 2 wherein the sterile
acid hydrolysis catalyst at an elevated pressure and aqueous solution of fermentable sugar is subjected to
temperature to provide a starch hydrolysate slurry fermentation to provide dilute aqueous ethanol.
 11
4,407,955
8. The process of claim 7 wherein the concentrated
ethanol is substantially dehydrated to provide anhy
drous ethanol.
9. The process of claim 1 or 2 further comprising the
steps of:
(d) diluting the water insoluble protein and oil result
ing from step (c) with water;
(e) separating water from the water insoluble protein
and oil resulting from step (d); and,
(f) recycling the water recovered in step (e) as a
source of water soluble carbohydrate for use in
hydrolysis step (c) and/or for preparing the starch
slurry for hydrolysis step (a).
12
10. The process of claim 9 wherein the dilution water
in step (b) is stillage from an ethanol concentration
facility.
11. The process of claim 1 or 2 wherein the aqueous
slurry of starch is prepared with stillage from an ethanol
concentration facility.
12. The process of claim 1 or 2 wherein stillage from
an ethanol concentration facility is used as a source of
water soluble non-fermentable carbohydrate for use in
10 hydrolysis step (c).
13. The process of claim 9 wherein the stillage is
contacted with an ion exchange resin prior to use in
forming the starch slurry.
14. The process of claim 10 wherein the stillage is
15 contacted with an ion exchange resin prior to use in
hydrolysis step (c).

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